JP2007284680A - Photocurable resin composition with excellent thermal conductivity - Google Patents

Photocurable resin composition with excellent thermal conductivity Download PDF

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JP2007284680A
JP2007284680A JP2007108866A JP2007108866A JP2007284680A JP 2007284680 A JP2007284680 A JP 2007284680A JP 2007108866 A JP2007108866 A JP 2007108866A JP 2007108866 A JP2007108866 A JP 2007108866A JP 2007284680 A JP2007284680 A JP 2007284680A
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epoxy resin
resin composition
photocurable resin
type epoxy
weight
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Jung Hyun Son
ジュンヒュン ソン
Jong Dai Park
ジョンダイ パク
In Seok Ahn
インソク アン
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Dongjin Semichem Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a versatile photocurable resin composition usable for production of organic light emitting diode (OLED), liquid crystal display (LCD) and flexible display, etc., by improving heat conductivity and barrier performance to steam. <P>SOLUTION: The photocurable resin composition comprises (a) 100 pts.wt. of an epoxy resin, (b) 0.01-20 pts.wt. of a photopolymerization initiator, (c) 0.01-10 pts.wt. of a coupling agent, (d) 0.01-120 pts.wt. of an inorganic filler and (e) 0.05-10 pts.wt. of a photo acid generating agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、光硬化性樹脂組成物に関し、特に、改善された熱伝導率により素子から発生した熱を容易に放出でき、水分に対するバリアー性に優れ、硬化時に発生する収縮を抑制することで、硬化物の接着強度などの物理的特性が低下されず、加熱なしに紫外線だけで硬化できる樹脂組成物であって、有機発光ダイオード(ＯＬＥＤ)、液晶ディスプレイ(ＬＣＤ)及びフレキシブルディスプレイ(flexible display)のようなディスプレイ製造に有用な光硬化性樹脂組成物に関する。   The present invention relates to a photocurable resin composition, in particular, it can easily release heat generated from the device due to improved thermal conductivity, has excellent barrier properties against moisture, and suppresses shrinkage that occurs during curing, It is a resin composition that can be cured only by ultraviolet rays without heating, without deteriorating physical properties such as adhesive strength of the cured product, and is used for organic light emitting diodes (OLED), liquid crystal displays (LCD), and flexible displays. It is related with the photocurable resin composition useful for such display manufacture.

エポキシ樹脂組成物は、金属等に対する接着力、せん断強度、引張強度等に優れるものの、エポキシ樹脂としての可溶性が不十分であり、剥離強度や耐衝撃強度が非常に低く、そのため亀裂、剥離等が発生しやすいという問題があり、これまで種々の改良がなされてきた。エポキシ樹脂組成物は、使用方法により、通常の一液型エポキシ樹脂組成物と、二液型エポキシ樹脂組成物とに大別される。一液型エポキシ樹脂組成物は、エポキシ樹脂に潜在性硬化剤を添加する方法であり、二液型エポキシ樹脂組成物は、ポリアミドアミン、脂肪族アミン等の硬化剤とエポキシ樹脂とを使用直前に混合して使用する方法である。このような二液型エポキシ樹脂組成物は、配合時の計量ミスによる硬化不良やポットライフが短いという問題がある。また、二液型エポキシ樹脂組成物にポリアミドアミン、脂肪族アミン等の硬化剤を用いる場合、硬化物の耐熱性が低く、不良が発生する恐れがある。よって、最近では、生産性の高い一液型エポキシ樹脂組成物の使用へと移行している。こうした一液型エポキシ樹脂は、特許文献１〜特許文献７等に開示されているが、これらは水分透過度が高くて樹脂の物性を低下させる恐れがあり、熱伝導度及び接着強度においても改善の余地がある。
日本特開２００５−２３９９２２号 日本特開２０００−２０４３２４号 日本特開２００５−３６０９５号 日本特開２００４−３５２７７１号 日本特開２００５−１０５１４８号 韓国特許公開２００３−０００７５１５号 韓国特許公開２００４−００７７８７９号 Although the epoxy resin composition is excellent in adhesion to metals, shear strength, tensile strength, etc., it is insufficiently soluble as an epoxy resin, and has very low peel strength and impact strength, so cracks, peel, etc. There is a problem that it easily occurs, and various improvements have been made so far. The epoxy resin composition is roughly classified into a normal one-pack type epoxy resin composition and a two-pack type epoxy resin composition depending on the method of use. The one-pack type epoxy resin composition is a method of adding a latent curing agent to the epoxy resin, and the two-pack type epoxy resin composition is used immediately before using a curing agent such as polyamidoamine and aliphatic amine and an epoxy resin. It is a method of mixing and using. Such a two-pack type epoxy resin composition has a problem of poor curing due to a measurement error at the time of blending and a short pot life. Moreover, when using hardening agents, such as a polyamidoamine and an aliphatic amine, in a two-pack type epoxy resin composition, the heat resistance of hardened | cured material is low and there exists a possibility that a defect may generate | occur | produce. Therefore, recently, there has been a shift to the use of a highly productive one-pack type epoxy resin composition. Such one-pack type epoxy resins are disclosed in Patent Literature 1 to Patent Literature 7 and the like, but these have high moisture permeability and may deteriorate the physical properties of the resin, and also improve the thermal conductivity and adhesive strength. There is room for.
Japanese Unexamined Patent Publication No. 2005-239922 Japanese Unexamined Patent Publication No. 2000-204324 Japanese Unexamined Patent Publication No. 2005-36095 Japanese Unexamined Patent Publication No. 2004-352771 Japanese Unexamined Patent Publication No. 2005-105148 Korean Patent Publication No. 2003-0007515 Korean Patent Publication No. 2004-0077879

よって、本発明の目的は、優れた引張強度及び接着強度を持ち、水分透過度が低く、硬化時に発生する収縮を防止できる光硬化性樹脂組成物を提供することにある。   Accordingly, an object of the present invention is to provide a photocurable resin composition having excellent tensile strength and adhesive strength, low moisture permeability, and capable of preventing shrinkage that occurs during curing.

本発明の他の目的は、熱伝導率を改善することで、素子から発生する熱の外部放出速度を増大させた光硬化性樹脂組成物を提供することにある。   Another object of the present invention is to provide a photocurable resin composition in which the external release rate of heat generated from the device is increased by improving the thermal conductivity.

上記目的を達成するために、本発明は、(ａ)１００重量部のエポキシ樹脂、(ｂ)０.０１〜２０重量部の光重合開始剤、(ｃ)０.０１〜１０重量部のカップリング剤、及び(ｄ)０.０１〜１２０重量部の無機充填剤を含む光硬化性樹脂組成物を提供する。また、本発明は、上記光硬化性樹脂組成物を光硬化して製造したディスプレイ材料を提供する。   In order to achieve the above object, the present invention comprises (a) 100 parts by weight of an epoxy resin, (b) 0.01 to 20 parts by weight of a photopolymerization initiator, and (c) 0.01 to 10 parts by weight of a cup. A photocurable resin composition comprising a ring agent and (d) 0.01 to 120 parts by weight of an inorganic filler is provided. Moreover, this invention provides the display material manufactured by photocuring the said photocurable resin composition.

以下、本発明をより詳細に説明すれば、次の通りである。
本発明による光硬化性樹脂組成物は、主成分として(ａ)エポキシ樹脂を含む。エポキシ樹脂の非限定例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、上記エポキシ樹脂のプレポリマー(prepolymer)、ポリエーテル変性エポキシ樹脂、シリコン変性エポキシ樹脂及び脂環式エポキシ樹脂のような上記エポキシ樹脂と他のポリマーとの共重合体などが挙げられ、上記エポキシ樹脂は、単独又は２種以上を混合して使用できる。特に、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂及びビフェニル型エポキシ樹脂は、耐熱性及び耐水性に優れるため好ましい。 Hereinafter, the present invention will be described in more detail as follows.
The photocurable resin composition according to the present invention contains (a) an epoxy resin as a main component. Non-limiting examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, glycidylamine type epoxy resins, dicyclopentadiene type epoxy resins, The above epoxy resins such as phenol novolac type epoxy resins, alicyclic epoxy resins, prepolymers of the above epoxy resins, polyether modified epoxy resins, silicon modified epoxy resins and alicyclic epoxy resins and other polymers. A copolymer etc. are mentioned, The said epoxy resin can be used individually or in mixture of 2 or more types. In particular, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resin are preferable because they are excellent in heat resistance and water resistance.

本発明による光硬化性樹脂組成物は、(ｂ)光重合開始剤を含む。光重合開始剤の非限定例としては、芳香族ジアゾニウム塩、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ヨードニウムアルミニウム塩、芳香族スルホニウムアルミニウム塩、メタロセン化合物又は鉄アレーン系化合物等を用いることができる。その中でも、光硬化性の観点から、芳香族スルホニウム塩が好ましく、特に芳香族スルホニウム・ヘキサフルオロリン酸塩化合物、芳香族スルホニウム・ヘキサフルオロアンチモネート化合物又はこれらの混合物を使用すると、硬化性や接着性等を向上させるため好ましい。上記光重合開始剤の含有量は、エポキシ基合計量１００重量部に対して０.０１〜２０重量部、好ましくは０.１〜１０重量部、より好ましくは１〜６重量部である。上記光重合開始剤の含有量が１０重量部を超過すると、反応に参加しない剰余分量が発生することになり、２０重量部を超過すると、上記剰余分量により組成物の物性が低下されるため好ましくない。また、本発明による光硬化性樹脂組成物の硬化物は、エポキシ変化率が８５％以上であるのが好ましい。   The photocurable resin composition according to the present invention contains (b) a photopolymerization initiator. Non-limiting examples of photopolymerization initiators include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, aromatic iodonium aluminum salts, aromatic sulfonium aluminum salts, metallocene compounds or iron arene compounds. it can. Of these, aromatic sulfonium salts are preferred from the viewpoint of photocurability, and particularly when aromatic sulfonium / hexafluorophosphate compounds, aromatic sulfonium / hexafluoroantimonate compounds or mixtures thereof are used, curability and adhesion It is preferable for improving the properties. Content of the said photoinitiator is 0.01-20 weight part with respect to 100 weight part of epoxy group total amount, Preferably it is 0.1-10 weight part, More preferably, it is 1-6 weight part. When the content of the photopolymerization initiator exceeds 10 parts by weight, a surplus amount that does not participate in the reaction is generated. When the content exceeds 20 parts by weight, the physical properties of the composition are decreased by the surplus amount, which is preferable. Absent. Moreover, it is preferable that the cured | curing material of the photocurable resin composition by this invention has an epoxy change rate of 85% or more.

本発明の光硬化性樹脂組成物に含まれる(ｃ)カップリング剤は、接着性を向上させるために用いられる。カップリング剤の非限定例としては、シラン系、チタン系のカップリング剤及びシリコン化合物などを単独又は２種以上を混合して使用できる。カップリング剤の含有量は、エポキシ樹脂１００重量部に対して０.０１〜１０重量部、好ましくは０.１〜５重量部、より好ましくは０.１〜２重量部である。カップリング剤の含有量が２重量部を超過すると、反応に参加しない剰余分量が発生することになり、１０重量部を超過すると、上記剰余分量により組成物の物性が低下されるため好ましくない。   The (c) coupling agent contained in the photocurable resin composition of the present invention is used to improve the adhesiveness. As a non-limiting example of the coupling agent, a silane-based or titanium-based coupling agent and a silicon compound can be used alone or in admixture of two or more. Content of a coupling agent is 0.01-10 weight part with respect to 100 weight part of epoxy resins, Preferably it is 0.1-5 weight part, More preferably, it is 0.1-2 weight part. When the content of the coupling agent exceeds 2 parts by weight, a surplus amount that does not participate in the reaction is generated. When the content exceeds 10 parts by weight, the physical properties of the composition are lowered by the surplus amount, which is not preferable.

本発明による光硬化性樹脂組成物に含まれる(ｄ)無機充填剤は、光透過性、水分に対するバリアー性及び熱伝導率を向上させ、硬化時の収縮防止のために添加するもので、シリカ、タルク、酸化マグネシウム(ＭｇＯ)、マイカ、モンモリロナイト、アルミナ、グラファイト、酸化ベリリウム、窒化アルミニウム、炭化ケイ素、ムライト、シリコンなどの板状又は球状の無機充填剤を使用でき、これらを単独又は混合して使用できる。特に、タルクは、水分に対するバリアー性及び光透過性に優れ、光硬化時に発生する収縮を防止する。アルミナ、グラファイト及びシリカは、熱伝導率が高いので、素子から発生する熱を外部に放出できる。よって、好ましくは、タルク、アルミナ、グラファイト及びシリカの中から選択された１種を単独に使用したり、例示した無機充填剤と混合して使用し、より好ましくは、アルミナ、グラファイト及びシリカの中から選択された１種とタルクとを混合して使用する。無機充填剤は、粒子サイズが０.１〜５０μｍであるものを使用でき、０.１〜１０μｍの小粒子及び５〜５０μｍの粒子等のような互いに異なるサイズを併用できる。無機充填剤の含有量は、エポキシ樹脂の１００重量部に対して０.０１〜１２０重量部、好ましくは０.１〜１１０重量部である。無機充填剤の含有量がエポキシ樹脂の１２０重量部を超過する場合、樹脂の重合反応を妨害して物性を低下させるため好ましくない。また、無機充填剤に置換基を導入して使用する場合、樹脂組成物の硬化物及びガラス間の接着力を増大させ、樹脂での分散特性及び接着力を増大させることができる。   The inorganic filler (d) contained in the photocurable resin composition according to the present invention is added to improve light transmittance, barrier property against moisture and thermal conductivity, and to prevent shrinkage during curing. , Talc, magnesium oxide (MgO), mica, montmorillonite, alumina, graphite, beryllium oxide, aluminum nitride, silicon carbide, mullite, silicon, and other plate-like or spherical inorganic fillers can be used. Can be used. In particular, talc is excellent in moisture barrier properties and light transmittance, and prevents shrinkage that occurs during photocuring. Since alumina, graphite, and silica have high thermal conductivity, heat generated from the element can be released to the outside. Therefore, preferably, one selected from talc, alumina, graphite and silica is used alone or mixed with the exemplified inorganic filler, and more preferably, among alumina, graphite and silica. 1 type selected from the above and talc are mixed and used. As the inorganic filler, those having a particle size of 0.1 to 50 μm can be used, and different sizes such as a small particle of 0.1 to 10 μm and a particle of 5 to 50 μm can be used in combination. Content of an inorganic filler is 0.01-120 weight part with respect to 100 weight part of an epoxy resin, Preferably it is 0.1-110 weight part. When the content of the inorganic filler exceeds 120 parts by weight of the epoxy resin, it is not preferable because the polymerization reaction of the resin is hindered and the physical properties are lowered. Moreover, when introduce | transducing a substituent to an inorganic filler and using it, the adhesive force between the hardened | cured material of a resin composition and glass can be increased, and the dispersion characteristic and adhesive force in resin can be increased.

本発明による光硬化性樹脂組成物は、上記(ｂ)光重合開始剤と共に(ｅ)光酸発生剤を必要に応じてさらに添加できる。光酸発生剤は、露光によりルイス酸又はブレンステッド酸を生成して、化学増幅作用を誘導するもので、光により酸を発生できる化合物であればよい。この光酸発生剤として、好ましくは、有機スルホン酸等の硫化塩系化合物、オニウム塩等のオニウム塩系化合物又はこれらの混合物を使用できる。これらの非限定例としては、フタルイミドトリフルオロメタンスルホネート、ジニトロベンジルトシレート、ｎ−デシルジスルホン、ナフチルイミドトリフルオロメタンスルホネート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアルセネート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルパラメトキシフェニルスルホニウムトリプレート、ジフェニルパラトルエニルスルホニウムトリプレート、ジフェニルパライソブチルフェニルスルホニウムトリプレート、トリフェニルスルホニウムヘキサフルオロアルセネート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムトリプレート、ジブチルナフチルスルホニウムトリプレート及びこれらの混合物が挙げられる。上記光酸発生剤の含有量は、上記エポキシ樹脂１００重量部に対して０.０５〜１０重量部であるのが好ましい。上記光酸発生剤の含有量が１０重量部を超過すると、組成物の遠紫外線の吸光度が増加し、酸が多量に発生するため、樹脂組成物の物性を低下させる恐れがある。   The photocurable resin composition according to the present invention may further contain (e) a photoacid generator together with the (b) photopolymerization initiator as required. The photoacid generator is a compound that generates a Lewis acid or a Bronsted acid by exposure to induce a chemical amplification action, and may be any compound that can generate an acid by light. As the photoacid generator, a sulfide compound such as organic sulfonic acid, an onium salt compound such as onium salt, or a mixture thereof can be preferably used. Non-limiting examples of these include phthalimide trifluoromethanesulfonate, dinitrobenzyl tosylate, n-decyl disulfone, naphthylimide trifluoromethanesulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroantimonate, diphenyl Paramethoxyphenylsulfonium triplate, diphenylparatoluenylsulfonium triplate, diphenylparaisobutylphenylsulfonium triplate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triplate, dibutylnaphthylsulfonium triplate Beauty mixtures thereof. The content of the photoacid generator is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin. When the content of the photoacid generator is more than 10 parts by weight, the composition absorbs far ultraviolet light and generates a large amount of acid, which may deteriorate the physical properties of the resin composition.

本発明によれば、光硬化性樹脂組成物は、優れた接着強度及び水分透過特性を持つと共に、熱硬化なしに光硬化だけで容易に硬化が行われるため、硬化時に発生する収縮を防止でき、特に、改善された熱伝導度により素子から発生する熱の外部放出速度を増大できるため、有機発光ダイオード、液晶ディスプレイ、フレキシブルディスプレイ等の製造に効果的に適用できる。   According to the present invention, the photocurable resin composition has excellent adhesive strength and moisture transmission characteristics, and can be easily cured only by photocuring without heat curing, so that shrinkage occurring during curing can be prevented. Particularly, since the external release rate of heat generated from the device can be increased due to the improved thermal conductivity, it can be effectively applied to the manufacture of organic light emitting diodes, liquid crystal displays, flexible displays and the like.

以下、実施例及び比較例を介して本発明を具体的に説明するが、これに限定されるものではない。下記の実施例及び比較例において各成分の含有量の単位は重量部である。   Hereinafter, the present invention will be described in detail through examples and comparative examples, but is not limited thereto. In the following Examples and Comparative Examples, the unit of content of each component is parts by weight.

（実施例１〜８及び比較例）光硬化性樹脂組成物
下記の表１に示すような成分及び含有量により、実施例１〜８及び比較例の光硬化性樹脂組成物を製造した。まず、エポキシ樹脂に陽イオン光重合開始剤、カップリング剤及び無機充填剤を添加し、均一に撹はんした後、脱泡を経て樹脂組成物を製造した。 Examples 1 to 8 and Comparative Examples Photocurable Resin Compositions Photocurable resin compositions of Examples 1 to 8 and Comparative Examples were produced according to the components and contents as shown in Table 1 below. First, a cationic photopolymerization initiator, a coupling agent, and an inorganic filler were added to an epoxy resin, stirred uniformly, and then defoamed to produce a resin composition.

エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂として日本エポキシ社製のＹＬ９８０を用い、陽イオン光重合開始剤は、芳香族スルホニウム塩として旭電化社製のＳＰ−１５０を用い、カップリング剤は、シランカップリング剤として信越化学社製のＫＢＭ−４０３を用い、アルミナは、それぞれの粒度が異なる製品として住友化学社製のＡＥＳ−１１Ｃ(平均粒度０.４μｍ)、ＡＬ−Ｍ４３(平均粒度２.７μｍ)、ＡＬ−Ｍ４１(平均粒度１.６μｍ)及びＡＭＳ−９(平均粒度道０.６μｍ)を用い、タルクは、日本タルク社製のＡＣＥ Ｐ−３を用いた。

Figure 2007284680
The epoxy resin is YL980 manufactured by Nippon Epoxy Co., Ltd. as a bisphenol A type epoxy resin, the cationic photopolymerization initiator is SP-150 manufactured by Asahi Denka Co., Ltd. as an aromatic sulfonium salt, and the coupling agent is a silane cup. KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd. was used as a ring agent, and alumina was manufactured by Sumitomo Chemical Co., Ltd. as AES-11C (average particle size 0.4 μm) and AL-M43 (average particle size 2.7 μm) as products having different particle sizes. AL-M41 (average particle size 1.6 μm) and AMS-9 (average particle size path 0.6 μm) were used, and ACE P-3 manufactured by Nippon Talc was used as the talc.
Figure 2007284680

（試験例１）水分透過度
バー塗工装置(bar applicator)を用いて異型処理されているＰＥＴ(Polyethylene terephthalate)フィルムの異型処理面に、実施例及び比較例で製造した光硬化性樹脂組成物を、１００ｍｍ＊１００ｍｍ＊１００μｍのサイズで塗工した後、６０００ｍＪ／ｃｍ２の紫外線(ＵＶ)を照射した。ＡＳＴＭ Ｆ１２４９の方法により、３８℃の温度及び９５％の相対湿度(ＲＨ)の条件において、２４時間水分投湿度を水分透過度測定器(製品名：ＰＥＲＭＡＴＲＡＮ−Ｗ ３／３３)で測定し、その結果を下記表２に示した。 (Test Example 1) A photocurable resin composition produced in Examples and Comparative Examples on the atypically treated surface of a PET (Polyethylene terephthalate) film that has been atypically treated using a moisture applicator bar applicator. Was coated with a size of 100 mm * 100 mm * 100 μm, and then irradiated with ultraviolet rays (UV) of 6000 mJ / cm 2 . According to the method of ASTM F1249, at a temperature of 38 ° C. and a relative humidity (RH) of 95%, the moisture throwing humidity was measured with a moisture permeability measuring device (product name: PERMATRAN-W 3/33). The results are shown in Table 2 below.

（試験例２）熱伝導度
バー塗工装置を用いて異型処理されているポリエチレンテレフタレートフィルムの異型処理面に、実施例及び比較例で製造した光硬化性樹脂組成物を、１００ｍｍ＊５０ｍｍ＊１００μｍのサイズになるように塗工した。ここに、６０００ｍＪ／ｃｍ２の紫外線を照射し、２４時間経過した後、ＱＴＭ(Quink Thermal Conductivity Meter)法を用いて熱伝導度測定器(製品名ＱＴＭ−５００)で測定し、その結果を下記表２に示した。 (Test Example 2) The photocurable resin compositions produced in Examples and Comparative Examples were applied to the modified surface of the polyethylene terephthalate film that has been subjected to atypical treatment using a thermal conductivity bar coating apparatus, 100 mm * 50 mm * 100 μm. The coating was made so that Here, after irradiating 6000 mJ / cm 2 of ultraviolet rays and 24 hours have passed, it was measured with a thermal conductivity meter (product name QTM-500) using the QTM (Quink Thermal Conductivity Meter) method, and the results were as follows: It is shown in Table 2.

（試験例３）接着強度
２５ｍｍ＊５０ｍｍ＊２.５ｍｍのガラスに厚さ５ｍｍで実施例及び比較例で製造した光硬化性樹脂組成物を塗工した後、その上に上記同じガラスを十字状に接着させた。ここに、６０００ｍＪ／ｃｍ２の紫外線を照射し、２４時間経過した後、接着強度測定器(製品名ＳＥＩＳＨＩＮ ＳＳ−３０ＷＤ)で測定し、その結果を下記表２に示した。

Figure 2007284680
(Test Example 3) After coating the photocurable resin compositions produced in Examples and Comparative Examples with a thickness of 5 mm on glass having an adhesive strength of 25 mm * 50 mm * 2.5 mm, the same glass was cross-shaped thereon. Glued to. This was irradiated with 6000 mJ / cm 2 of ultraviolet rays, and after 24 hours, it was measured with an adhesive strength measuring device (product name: SEISHIN SS-30WD). The results are shown in Table 2 below.
Figure 2007284680

上記表２を参照すれば、本発明による無機充填剤を一つ以上含む実施例は、無機充填剤を使用しない比較例に比べて、水分透過度が低くて水分に対するバリアー性に優れることが分かる。熱伝導度では、無機充填剤を２０重量部使用した実施例１〜実施例３の場合は比較例と類似しているが、無機充填剤を４０重量部以上使用した実施例４〜実施例８の場合は比較例よりも高い熱伝導度を示した。特に、無機充填剤として平均粒度が異なるアルミナを混合して９０重量部以上使用した実施例６〜実施例８は、非常に優れた熱伝導度を示した。接着強度では、実施例１を除いた本発明による実施例は比較例よりも優れ、特にアルミナＡＬ−Ｍ４３、ＡＬ−Ｍ４１、ＡＭＳ−９を同時に使用した実施例７及び８の場合は接着強度に優れた。実施例７及び実施例８は、タルク以外の成分及び造成が一致する。よって、タルクの含有により水分透過度及び接着強度は多少向上するが、熱伝導度は多少低下されることが分かる。   Referring to Table 2 above, it can be seen that Examples including one or more inorganic fillers according to the present invention have a low moisture permeability and excellent barrier properties against moisture compared to Comparative Examples not using inorganic fillers. . In terms of thermal conductivity, Examples 1 to 3 using 20 parts by weight of an inorganic filler are similar to Comparative Examples, but Examples 4 to 8 using 40 parts by weight or more of an inorganic filler are used. In the case of, the thermal conductivity was higher than that of the comparative example. In particular, Examples 6 to 8 in which 90 parts by weight or more of aluminas having different average particle sizes were mixed as inorganic fillers showed very excellent thermal conductivity. In the adhesive strength, the examples according to the present invention excluding Example 1 are superior to the comparative examples, and in particular, in the case of Examples 7 and 8 using alumina AL-M43, AL-M41 and AMS-9 at the same time, the adhesive strength is improved. outstanding. In Example 7 and Example 8, the components and formation other than talc coincide. Therefore, it can be seen that the moisture permeability and the adhesive strength are slightly improved by the inclusion of talc, but the thermal conductivity is somewhat decreased.

Claims (9)

(ａ)１００重量部のエポキシ樹脂
(ｂ)０.０１〜２０重量部の光重合開始剤
(ｃ)０.０１〜１０重量部のカップリング剤、及び
(ｄ)０.０１〜１２０重量部の無機充填剤を含む、光硬化性樹脂組成物。 (a) 100 parts by weight of epoxy resin
(b) 0.01 to 20 parts by weight of a photopolymerization initiator
(c) 0.01 to 10 parts by weight of a coupling agent, and
(d) A photocurable resin composition comprising 0.01 to 120 parts by weight of an inorganic filler. (ｅ)０.０５〜１０重量部の光酸発生剤をさらに含む、請求項１に記載の光硬化性樹脂組成物。   (e) The photocurable resin composition according to claim 1, further comprising 0.05 to 10 parts by weight of a photoacid generator. (ａ)エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、これらエポキシ樹脂のプレポリマー、ポリエーテル変性エポキシ樹脂、シリコン変性エポキシ樹脂及びこれらエポキシ樹脂と他のポリマーとの共重合体からなる群から選択された１種又は２種以上の混合物である、請求項１に記載の光硬化性樹脂組成物。   (a) Epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, glycidylamine type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac Type epoxy resin, alicyclic epoxy resin, prepolymer of these epoxy resins, polyether-modified epoxy resin, silicon-modified epoxy resin and one kind selected from the group consisting of copolymers of these epoxy resins and other polymers or The photocurable resin composition of Claim 1 which is a 2 or more types of mixture. (ｂ)光重合開始剤は、芳香族ジアゾニウム塩、芳香族スルホニウム塩、芳香族ヨードニウム塩、芳香族ヨードニウムアルミニウム塩、芳香族スルホニウムアルミニウム塩、メタロセン化合物及び鉄アレーン系化合物からなる群から選択されるものである、請求項１に記載の光硬化性樹脂組成物。   (b) The photopolymerization initiator is selected from the group consisting of aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, aromatic iodonium aluminum salts, aromatic sulfonium aluminum salts, metallocene compounds and iron arene compounds. The photocurable resin composition according to claim 1, which is a product. (ｃ)カップリング剤は、シラン系のカップリング剤、チタン系のカップリング剤及びシリコン化合物からなる群から選択された１種又は２種以上の混合物である、請求項１に記載の光硬化性樹脂組成物。   (c) The photocuring according to claim 1, wherein the coupling agent is one or a mixture of two or more selected from the group consisting of a silane coupling agent, a titanium coupling agent, and a silicon compound. Resin composition. (ｄ)無機充填剤は、シリカ、タルク、酸化マグネシウム、マイカ、モンモリロナイト、アルミナ、グラファイト、酸化ベリリウム、窒化アルミニウム、炭化ケイ素、ムライト及びシリコンからなる群から選択された１種又は２種以上の混合物である、請求項１に記載の光硬化性樹脂組成物。   (d) The inorganic filler is one or a mixture of two or more selected from the group consisting of silica, talc, magnesium oxide, mica, montmorillonite, alumina, graphite, beryllium oxide, aluminum nitride, silicon carbide, mullite, and silicon. The photocurable resin composition according to claim 1, wherein (ｄ)無機充填剤は、アルミナ、グラファイト及びシリカからなる群で選択された１種とタルクとの混合物である、請求項６に記載の光硬化性樹脂組成物。   The photocurable resin composition according to claim 6, wherein (d) the inorganic filler is a mixture of one type selected from the group consisting of alumina, graphite and silica and talc. (ｅ)光酸発生剤は、硫化塩系化合物又はオニウム塩系化合物である、請求項２に記載の光硬化性樹脂組成物。   (e) The photoacid generator is a photocurable resin composition according to claim 2, wherein the photoacid generator is a sulfide salt compound or an onium salt compound. 請求項１〜請求項８の何れか一つに記載の光硬化性樹脂組成物を光硬化して製造したディスプレイ材料。   The display material manufactured by photocuring the photocurable resin composition as described in any one of Claims 1-8.
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